WO2000010911A1 - Method and apparatus for injecting a liquid hydrocarbon fuel into a fuel cell power plant reformer - Google Patents

Method and apparatus for injecting a liquid hydrocarbon fuel into a fuel cell power plant reformer Download PDF

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Publication number
WO2000010911A1
WO2000010911A1 PCT/US1999/018875 US9918875W WO0010911A1 WO 2000010911 A1 WO2000010911 A1 WO 2000010911A1 US 9918875 W US9918875 W US 9918875W WO 0010911 A1 WO0010911 A1 WO 0010911A1
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Prior art keywords
fuel
steam
stream
processing assembly
droplets
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PCT/US1999/018875
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French (fr)
Inventor
Donald F. Szydlowski
Richard A. Sederquist
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International Fuel Cells, Llc
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Publication date
Application filed by International Fuel Cells, Llc filed Critical International Fuel Cells, Llc
Priority to JP2000566190A priority Critical patent/JP2002523862A/en
Priority to EP99945099A priority patent/EP1109736A4/en
Priority to AU57788/99A priority patent/AU5778899A/en
Priority to BR9914286-4A priority patent/BR9914286A/en
Publication of WO2000010911A1 publication Critical patent/WO2000010911A1/en

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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
    • C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
    • C01B3/38—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts
    • C01B3/382—Multi-step processes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01B—BOILING; BOILING APPARATUS ; EVAPORATION; EVAPORATION APPARATUS
    • B01B1/00—Boiling; Boiling apparatus for physical or chemical purposes ; Evaporation in general
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01B—BOILING; BOILING APPARATUS ; EVAPORATION; EVAPORATION APPARATUS
    • B01B1/00—Boiling; Boiling apparatus for physical or chemical purposes ; Evaporation in general
    • B01B1/005—Evaporation for physical or chemical purposes; Evaporation apparatus therefor, e.g. evaporation of liquids for gas phase reactions
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/26—Nozzle-type reactors, i.e. the distribution of the initial reactants within the reactor is effected by their introduction or injection through nozzles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
    • B01J8/0278—Feeding reactive fluids
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
    • C01B3/323—Catalytic reaction of gaseous or liquid organic compounds other than hydrocarbons with gasifying agents
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
    • C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
    • C01B3/38—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/06—Combination of fuel cells with means for production of reactants or for treatment of residues
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00049—Controlling or regulating processes
    • B01J2219/00051—Controlling the temperature
    • B01J2219/00074—Controlling the temperature by indirect heating or cooling employing heat exchange fluids
    • B01J2219/00119—Heat exchange inside a feeding nozzle or nozzle reactor
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00049—Controlling or regulating processes
    • B01J2219/00162—Controlling or regulating processes controlling the pressure
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00049—Controlling or regulating processes
    • B01J2219/00182—Controlling or regulating processes controlling the level of reactants in the reactor vessel
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00049—Controlling or regulating processes
    • B01J2219/00245—Avoiding undesirable reactions or side-effects
    • B01J2219/00247—Fouling of the reactor or the process equipment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00049—Controlling or regulating processes
    • B01J2219/00245—Avoiding undesirable reactions or side-effects
    • B01J2219/00252—Formation of deposits other than coke
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/02—Processes for making hydrogen or synthesis gas
    • C01B2203/0205—Processes for making hydrogen or synthesis gas containing a reforming step
    • C01B2203/0227—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step
    • C01B2203/0244—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step the reforming step being an autothermal reforming step, e.g. secondary reforming processes
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/06—Integration with other chemical processes
    • C01B2203/066—Integration with other chemical processes with fuel cells
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/08—Methods of heating or cooling
    • C01B2203/0805—Methods of heating the process for making hydrogen or synthesis gas
    • C01B2203/0838—Methods of heating the process for making hydrogen or synthesis gas by heat exchange with exothermic reactions, other than by combustion of fuel
    • C01B2203/0844—Methods of heating the process for making hydrogen or synthesis gas by heat exchange with exothermic reactions, other than by combustion of fuel the non-combustive exothermic reaction being another reforming reaction as defined in groups C01B2203/02 - C01B2203/0294
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/12—Feeding the process for making hydrogen or synthesis gas
    • C01B2203/1205—Composition of the feed
    • C01B2203/1211—Organic compounds or organic mixtures used in the process for making hydrogen or synthesis gas
    • C01B2203/1235—Hydrocarbons
    • C01B2203/1247—Higher hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/12—Feeding the process for making hydrogen or synthesis gas
    • C01B2203/1258—Pre-treatment of the feed
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/12—Feeding the process for making hydrogen or synthesis gas
    • C01B2203/1276—Mixing of different feed components
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/12—Feeding the process for making hydrogen or synthesis gas
    • C01B2203/1288—Evaporation of one or more of the different feed components
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/14—Details of the flowsheet
    • C01B2203/142—At least two reforming, decomposition or partial oxidation steps in series
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/80—Aspect of integrated processes for the production of hydrogen or synthesis gas not covered by groups C01B2203/02 - C01B2203/1695
    • C01B2203/82—Several process steps of C01B2203/02 - C01B2203/08 integrated into a single apparatus
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

Definitions

  • the present invention relates to a system for reforming a raw liquid hydrocarbon fuel, and in a preferred embodiment, to a liquid fuel injector assembly for an autothermal fuel reformer which is operable to limit or eliminate carbon deposition from the vaporization of liquid fuel as the latter passes into the vaporizer before entering the reformer.
  • Autothermal hydrocarbon fuel reformers are known for the purpose of converting a raw hydrocarbon fuel to a hydrogen-enriched fuel which, with some additional cleanup, is suitable for use as a fuel gas for a fuel ceil power plant.
  • autothermal reformers are employed instead of conventional thermal steam reformers when heavier hydrocarbons are to be processed.
  • Feed stocks such as gasoline or the like are better suited to be reformed by an autothermal reformer.
  • the autothermal reformer is supplied with a mixture of air, steam and the raw fuel, and will catalytically convert this mixture to a hydrogen-rich processed fuel gas.
  • most hydrocarbon feed stocks can be reformed to a hydrogen-enriched fuel cell reactant fuel by passing the air, steam and raw fuel over a catalyst bed in the reformer, wherein the following typical reaction takes place:
  • the reformer catalyst can be poisoned by constituents in the liquid raw fuel, particularly sulfur.
  • carbon deposits can form in the vaporizer when the liquid raw fuel gas comes into contact with hot vaporizer surfaces before it vaporizes, thus fouling the vaporizer. Such carbon deposits would block vaporizer passages into the reformer, thus rendering the vaporizer unusable.
  • the problem of carbon deposition in the vaporizer is particularly exacerbated when the raw fuel being processed is a liquid fuel, such as gasoline, fuel oil, kerosene, naphtha, diesel fuel, or the like.
  • liquid raw fuels such as gasoline, diesel fuel, or the like, which are commonly available at gas stations, as the process fuel which is to be reformed for use in a fuel cell power plant.
  • a mobile vehicle such as an automobile, truck, bus, or the like could be electrically powered by electricity produced by an on board fuel cell power plant which employs such a liquid fuel as its hydrogen source.
  • an on board fuel cell power plant which employs such a liquid fuel as its hydrogen source.
  • This invention relates to a liquid fuel atomizer which creates very fine droplets. These droplets can then easily be vaporized by a hot gas stream in a distance of only a few inches after exiting the atomizer. This is a desirable attribute of the invention since it keeps the fuel droplets from contacting the hot metal surfaces of the vaporizer, thus preventing carbon formation in the vaporizer and the vaporizer plugging which would result.
  • the proposed fuel atomizer comprises a small tube into which the liquid fuel is introduced along with an atomizing vapor stream such as steam. It is desirable to have the atomizing vapor stream velocity in the one hundred to five hundred ft sec range.
  • the fuel-steam stream is injected into the mixing chamber through a small bore tube at sufficiently high velocities so as to create an annular stream of the liquid fuel within the atomizer tube which surrounds a core of steam.
  • the thickness of the annular fuel stream is a function of the fuel velocity-to-steam velocity ratio, and the ratio of fuel to steam in the fuel-steam mixture.
  • the liquid fuel forms a thin annular film adjacent to the inside wall of the tube from which the atomized fuel droplets are formed by the extremely high shearing forces created by the atomizing vapor stream.
  • the resultant droplets are quite small, and have a mean droplet diameter of less than ten microns.
  • This composite stream is injected into an outer annular mixture of super heated steam, the temperature of which is about 538° C (1000° F), or hot steam and air, which essentially instantaneously vaporizes the liquid fuel droplets exiting from the atomizer tube.
  • the liquid fuel component of the fuel-steam mixture can be vaporized by the hot steam within one inch to three inches after leaving the atomizer tube.
  • the aforesaid fuel atomizer system was used in conjunction with an autothermal reformer test rig to evaluate the reformer in a three hundred hour test run.
  • the atomizer was used to process the jet fuel JP8 at a flow rate of 40.0 Kg per hour (gph) (8.8 pounds per hour).
  • the atomizer was able to produce a fine droplet stream when the fuel was injected into a high velocity saturated steam core which had a flow rate of 1000 gph (2.2 pph).
  • the atomizer was coupled to a vaporizer section in the test rig which completely vaporized fuel droplets using super heated steam at a flow rate of 13.6 Kgph (30.0 pph) at 482°C (900°F). After three hundred hours of testing, a post test inspection of the vaporizer showed no trace of carbon particles inside of the vaporizer.
  • This invention thus relates to a method and apparatus for limiting carbon formation in a vaporizer section leading to a reformer, preferably an autothermal reformer, which is used to process a liquid fuel such as gasoline, or the like.
  • FIG. 1 is a schematic view of a liquid fuel autothermal reformer which employs the method and apparatus of this invention.
  • Fig. 2 is a somewhat schematic sectional view of an embodiment of a liquid fuel- steam injector tube and steam atomizing assembly which is formed in accordance with this invention.
  • Fig. 1 is a schematic view of a liquid fuel atomizing/vaporizing and fuel processing system, which is denoted generally by the numeral 2, and which is suitable for use in a vehicle such as an automobile, and in fuel processing systems.
  • the fuel being processed can be gasoline, diesel fuel, naphtha or the like liquid fuels.
  • the system 2 includes a fuel atomizer section 4 in which a liquid fuel stream is atomized and converted to droplets having a size or diameter of less than about ten microns.
  • the liquid fuel is injected into the atomizer section 4 via a fuel injection tube 6 and steam is injected into the atomizer section 4 via a steam injection tube 8.
  • the fuel and steam form a compound flow pattern in a tube section 9 wherein the steam fraction forms the core of the pattern, and the fuel forms an outer annulus in the pattern.
  • a supply of super heated steam (about 538°C) is injected into the fuel vaporizer chamber 10 through line 12.
  • the steam from the line 12 is utilized to vaporize the atomized fuel droplets which are ejected from the tube 9.
  • Fuel/steam vapor which exits the chamber 10 is admixed in a mixer chamber 14 with air which is injected into the chamber 14 via a line 16.
  • the vaporized fuel-air mixture then enters a reformer 18, which is preferably an autothermal reformer (ATR), where the fuel is converted into a hydrogen enriched gas.
  • ATR autothermal reformer
  • FIG. 2 shows details of one embodiment of the fuel-steam atomizer section 4 and the fuel vaporizer-mixing chamber portion 10 of the system 2 of FIG. 1.
  • the atomizer tube 9 projects from the atomizer section 4 and is operable to produce a composite jet of steam S and a film of liquid fuel F, with the steam component S forming the core of the composite jet, and the fuel film component F forming an outer annulus of the composite jet. It is desirable to minimize the thickness of the fuel annulus F so that the liquid fuel droplets D leaving the end of the tube 9 can be quickly vaporized in the stream of super heated steam, the latter of which is denoted by the arrows A, after the droplets D leave the atomizer tube 9.
  • the velocity of the fuel film F and steam S in the atomizer tube 9 should preferably be kept in the range of about 15 to about 153 m/sec (50 to about 500 ft/sec).
  • warm (about 52°C) liquid fuel and a small amount of saturated steam are fed through an atomizer tube 9 having a bore diameter of about 0.1397 cm (0.055 inch) at the aforesaid high velocities, the fuel component F forms a film on the inner wall of the tube 9 in the fuel-steam stream, and the steam S forms the core of the fuel-steam stream, as seen in FIG. 2.
  • the steam component S has a velocity of about 37 m/sec (120 ft/sec) which is typically twice that of the fuel component F in the fuel-steam stream.
  • the super heated steam A almost instantaneously vaporizes the fuel component in the composite stream, in part due to the extremely small droplet size of the fuel droplets D.
  • the fuel droplets D With an atomizing heated steam stream velocity of 153 m/sec (500 ft/sec), and about a three micron fuel film thickness, the fuel droplets D will vaporize in the super heated steam within about 2.5 cm (1 in.) of being ejected from the injection tube 9.
  • the dwell time of the liquid fuel in the vaporizer 10 is only about 0.2 milliseconds. With such a short dwell time, there will be little or no interaction between the liquid fuel droplets D and components of the vaporizer 10. Therefore, the formation of carbon deposits resulting from the liquid fuel droplets D contacting components of the system 2 is greatly restricted or eliminated.
  • the method and apparatus of this invention enables the use of a greatly reduced liquid fuel vaporizer size.
  • the invention also allows the mixing of a liquid fuel and steam composite stream with super heated steam which results in a vaporized fuel that is suitable for further mixing with an air supply.
  • the vaporized fuel and air mixture is then fed into an autothermal reformer to process the atomized fuel and air mixture into a hydrogen rich fuel stream for a fuel cell power plant.

Abstract

A fuel atomizer (4) for a liquid hydrocarbon fuel reformer/processor (2) creates a high velocity atomized stream of a liquid fuel and stream, wherein the liquid fuel is quickly vaporized so as to limit carbon deposition from the fuel on the surfaces of the fuel vaporizer (10). The injector includes a small diameter fuel injection tube (6) through which the liquid fuel and steam mixture is ejected at relatively high velocities. The liquid fuel forms an annular film which surrounds a steam core in the tube, which film and steam core composite are ejected from the tube into a stream of super heated steam, or steam and air, provided via an input (16). The stream of super heated steam substantially instantaneously vaporizes the fuel droplets from the film after the latter leaves the injection tube.

Description

Description
Method and Apparatus for Injecting a Liquid Hydrocarbon Fuel into a Fuel Cell Power
Plant Reformer
Technical Field The present invention relates to a system for reforming a raw liquid hydrocarbon fuel, and in a preferred embodiment, to a liquid fuel injector assembly for an autothermal fuel reformer which is operable to limit or eliminate carbon deposition from the vaporization of liquid fuel as the latter passes into the vaporizer before entering the reformer.
Background of the Invention
Autothermal hydrocarbon fuel reformers are known for the purpose of converting a raw hydrocarbon fuel to a hydrogen-enriched fuel which, with some additional cleanup, is suitable for use as a fuel gas for a fuel ceil power plant. Typically, autothermal reformers are employed instead of conventional thermal steam reformers when heavier hydrocarbons are to be processed. Feed stocks such as gasoline or the like are better suited to be reformed by an autothermal reformer. The autothermal reformer is supplied with a mixture of air, steam and the raw fuel, and will catalytically convert this mixture to a hydrogen-rich processed fuel gas. In theory, most hydrocarbon feed stocks can be reformed to a hydrogen-enriched fuel cell reactant fuel by passing the air, steam and raw fuel over a catalyst bed in the reformer, wherein the following typical reaction takes place:
CH2 + 2.55 H2O + 0.35 (O2 + 4N2) → CO2 + 2.3 H2 + 1.4 N2 + 1.25 H2O.
In operation, however, a number of factors can inhibit the ability of the reformer to perform its desired function. The reformer catalyst can be poisoned by constituents in the liquid raw fuel, particularly sulfur. In addition, carbon deposits can form in the vaporizer when the liquid raw fuel gas comes into contact with hot vaporizer surfaces before it vaporizes, thus fouling the vaporizer. Such carbon deposits would block vaporizer passages into the reformer, thus rendering the vaporizer unusable. The problem of carbon deposition in the vaporizer is particularly exacerbated when the raw fuel being processed is a liquid fuel, such as gasoline, fuel oil, kerosene, naphtha, diesel fuel, or the like. In certain applications, such as in mobile fuel cell-powered applications, it would be desirable to be able to utilize liquid raw fuels such as gasoline, diesel fuel, or the like, which are commonly available at gas stations, as the process fuel which is to be reformed for use in a fuel cell power plant. In this way, a mobile vehicle such as an automobile, truck, bus, or the like could be electrically powered by electricity produced by an on board fuel cell power plant which employs such a liquid fuel as its hydrogen source. In order to obtain such a result, however, one would have to deal with, among other things, the problem of carbon deposition from the liquid fuel in the vaporizer.
Disclosure of the Invention
This invention relates to a liquid fuel atomizer which creates very fine droplets. These droplets can then easily be vaporized by a hot gas stream in a distance of only a few inches after exiting the atomizer. This is a desirable attribute of the invention since it keeps the fuel droplets from contacting the hot metal surfaces of the vaporizer, thus preventing carbon formation in the vaporizer and the vaporizer plugging which would result.
The proposed fuel atomizer comprises a small tube into which the liquid fuel is introduced along with an atomizing vapor stream such as steam. It is desirable to have the atomizing vapor stream velocity in the one hundred to five hundred ft sec range. The fuel-steam stream is injected into the mixing chamber through a small bore tube at sufficiently high velocities so as to create an annular stream of the liquid fuel within the atomizer tube which surrounds a core of steam. The thickness of the annular fuel stream is a function of the fuel velocity-to-steam velocity ratio, and the ratio of fuel to steam in the fuel-steam mixture. The liquid fuel forms a thin annular film adjacent to the inside wall of the tube from which the atomized fuel droplets are formed by the extremely high shearing forces created by the atomizing vapor stream. The resultant droplets are quite small, and have a mean droplet diameter of less than ten microns. This composite stream is injected into an outer annular mixture of super heated steam, the temperature of which is about 538° C (1000° F), or hot steam and air, which essentially instantaneously vaporizes the liquid fuel droplets exiting from the atomizer tube. For example, the liquid fuel component of the fuel-steam mixture can be vaporized by the hot steam within one inch to three inches after leaving the atomizer tube. By essentially instantaneously vaporizing the liquid fuel, deposition of carbon from the liquid fuel on components of the reformer can be minimized. The aforesaid fuel atomizer system was used in conjunction with an autothermal reformer test rig to evaluate the reformer in a three hundred hour test run. The atomizer was used to process the jet fuel JP8 at a flow rate of 40.0 Kg per hour (gph) (8.8 pounds per hour). The atomizer was able to produce a fine droplet stream when the fuel was injected into a high velocity saturated steam core which had a flow rate of 1000 gph (2.2 pph). The atomizer was coupled to a vaporizer section in the test rig which completely vaporized fuel droplets using super heated steam at a flow rate of 13.6 Kgph (30.0 pph) at 482°C (900°F). After three hundred hours of testing, a post test inspection of the vaporizer showed no trace of carbon particles inside of the vaporizer.
This invention thus relates to a method and apparatus for limiting carbon formation in a vaporizer section leading to a reformer, preferably an autothermal reformer, which is used to process a liquid fuel such as gasoline, or the like.
It is therefore an object of this invention to provide a method and apparatus for injecting a liquid fuel into a fuel vaporizer which results in minimal carbon deposition in the vaporizer.
It is a further object of this invention to provide a method and apparatus of the character described wherein the liquid fuel stock is essentially instantaneously vaporized upon entry into the vaporizer.
It is an additional object of this invention to provide a method and apparatus of the character described wherein a mixture of liquid fuel and steam is injected into the vaporizer in the form of a fuel-steam composite having atomized fuel droplets which have a mean diameter of less than about ten microns.
It is another object of this invention to provide a method and apparatus of the character described wherein the fuel-steam stream is entrained in a super heated steam-air stream which vaporizes the fuel component of the fuel-steam stream as the latter enters the vaporizer.
These and other objects and advantages of the invention will become more readily apparent from the following detailed description thereof when taken in conjunction with the accompanying drawings in which: Brief Description of the Drawings Fig. 1 is a schematic view of a liquid fuel autothermal reformer which employs the method and apparatus of this invention; and
Fig. 2 is a somewhat schematic sectional view of an embodiment of a liquid fuel- steam injector tube and steam atomizing assembly which is formed in accordance with this invention.
Specific Embodiments for Carrying Out the Invention Referring now to the drawings, Fig. 1 is a schematic view of a liquid fuel atomizing/vaporizing and fuel processing system, which is denoted generally by the numeral 2, and which is suitable for use in a vehicle such as an automobile, and in fuel processing systems. The fuel being processed, as noted above, can be gasoline, diesel fuel, naphtha or the like liquid fuels. The system 2 includes a fuel atomizer section 4 in which a liquid fuel stream is atomized and converted to droplets having a size or diameter of less than about ten microns. The liquid fuel is injected into the atomizer section 4 via a fuel injection tube 6 and steam is injected into the atomizer section 4 via a steam injection tube 8. The fuel and steam form a compound flow pattern in a tube section 9 wherein the steam fraction forms the core of the pattern, and the fuel forms an outer annulus in the pattern. A supply of super heated steam (about 538°C) is injected into the fuel vaporizer chamber 10 through line 12. The steam from the line 12 is utilized to vaporize the atomized fuel droplets which are ejected from the tube 9. Fuel/steam vapor which exits the chamber 10 is admixed in a mixer chamber 14 with air which is injected into the chamber 14 via a line 16. The vaporized fuel-air mixture then enters a reformer 18, which is preferably an autothermal reformer (ATR), where the fuel is converted into a hydrogen enriched gas.
FIG. 2 shows details of one embodiment of the fuel-steam atomizer section 4 and the fuel vaporizer-mixing chamber portion 10 of the system 2 of FIG. 1. The atomizer tube 9 projects from the atomizer section 4 and is operable to produce a composite jet of steam S and a film of liquid fuel F, with the steam component S forming the core of the composite jet, and the fuel film component F forming an outer annulus of the composite jet. It is desirable to minimize the thickness of the fuel annulus F so that the liquid fuel droplets D leaving the end of the tube 9 can be quickly vaporized in the stream of super heated steam, the latter of which is denoted by the arrows A, after the droplets D leave the atomizer tube 9. This goal is accomplished by a proper combination of several atomizer parameters, namely, tube diameter, fuel/steam velocity ratio, steam temperature and pressure, and the liquid fuel density. The velocity of the fuel film F and steam S in the atomizer tube 9 should preferably be kept in the range of about 15 to about 153 m/sec (50 to about 500 ft/sec). When warm (about 52°C) liquid fuel and a small amount of saturated steam are fed through an atomizer tube 9 having a bore diameter of about 0.1397 cm (0.055 inch) at the aforesaid high velocities, the fuel component F forms a film on the inner wall of the tube 9 in the fuel-steam stream, and the steam S forms the core of the fuel-steam stream, as seen in FIG. 2. The steam component S has a velocity of about 37 m/sec (120 ft/sec) which is typically twice that of the fuel component F in the fuel-steam stream. When the fuel-steam stream is injected into the super heated steam stream A from the line 12, the super heated steam A almost instantaneously vaporizes the fuel component in the composite stream, in part due to the extremely small droplet size of the fuel droplets D.
With an atomizing heated steam stream velocity of 153 m/sec (500 ft/sec), and about a three micron fuel film thickness, the fuel droplets D will vaporize in the super heated steam within about 2.5 cm (1 in.) of being ejected from the injection tube 9. Thus at the velocities specified above, the dwell time of the liquid fuel in the vaporizer 10 is only about 0.2 milliseconds. With such a short dwell time, there will be little or no interaction between the liquid fuel droplets D and components of the vaporizer 10. Therefore, the formation of carbon deposits resulting from the liquid fuel droplets D contacting components of the system 2 is greatly restricted or eliminated.
It will be appreciated that the method and apparatus of this invention enables the use of a greatly reduced liquid fuel vaporizer size. The invention also allows the mixing of a liquid fuel and steam composite stream with super heated steam which results in a vaporized fuel that is suitable for further mixing with an air supply. The vaporized fuel and air mixture is then fed into an autothermal reformer to process the atomized fuel and air mixture into a hydrogen rich fuel stream for a fuel cell power plant.
Since many changes and variations of the disclosed embodiment of the invention may be made without departing from the inventive concept, it is not intended to limit the invention otherwise than as required by the appended claims.
What is claimed is:

Claims

Claims
1. A fuel processing assembly for use in connection with a fuel cell power plant, said fuel processing assembly comprising: a) a fuel vaporizing chamber; b) a fuel atomizing section for directing a mixture of atomized fuel droplets and steam toward said fuel vaporizing chamber; c) a line for injecting a super heated vaporizing stream into said fuel processing assembly, said line being located between said atomizing section and said vaporizing chamber whereby a super heated vaporizing stream can be injected into said mixture of fuel droplets and steam so as to vaporize said fuel droplets in said mixture of fuel droplets and steam; and d) a fuel reformer located downstream of said fuel vaporizing chamber for receiving vaporized fuel from said fuel vaporizing chamber.
2. The fuel processing assembly of Claim 1 wherein said atomizing section is operable to produce a fuel-steam mixture wherein the atomized fuel droplets form from an annular film which surrounds a core of steam.
3. The fuel processing assembly of Claim 2 wherein the fuel film moves at a velocity which is about one half of the velocity of the steam core.
4. The fuel processing assembly of Claim 3 wherein the respective velocities of the fuel film and the steam core are in the range of about 15 to about 153 m/sec.
5. The fuel processing assembly of Claim 4 wherein said atomized fuel droplets have a mean diameter of less than about ten microns.
6. The fuel processing assembly of Claim 5 wherein said super heated vaporizing stream is super heated steam or a mixture of super heated steam and air.
7. The fuel processing assembly of Claim 6 wherein said super heated vaporizing stream is heated to a temperature of about 540┬░C.
8. The fuel processing assembly of Claim 7 wherein said fuel reformer is an autothermal reformer.
9. A fuel processing assembly for use in connection with a fuel cell power plant, said fuel processing assembly comprising: a) a fuel vaporizing chamber; b) a fuel atomizing section leading to said fuel vaporizing chamber; c) a first line for injecting a hydrocarbon fuel stream into said atomizing section; d) a second line for injecting steam into said atomizing section, said second line being located downstream of said first line; e) a third line for injecting super heated steam into said fuel processing assembly, said third line being located downstream of said second line and immediately upstream of said vaporizing chamber; and f) a fuel reformer located downstream of said vaporizing chamber for receiving vaporized fuel from said vaporizing chamber.
10. The fuel processing assembly of Claim 9 further comprising an air injection line down stream of the vaporizer for mixing air with the vaporized fuel and feeding an autothermal reformer.
11. A method for processing a liquid hydrocarbon fuel so as to render the fuel suitable for use in powering a fuel cell power plant and also limit carbon deposition on fuel processing components, said method comprising the steps of: a) providing a fuel vaporizing chamber; b) forming and directing a mixture of atomized fuel droplets and steam toward said fuel vaporizing chamber; c) injecting a super heated vaporizing stream into said fuel processing assembly, said line being located between said atomizing section and said vaporizing chamber whereby a super heated vaporizing stream can be injected into said mixture of fuel droplets and steam so as to vaporize said fuel droplets in said mixture of fuel droplets and steam; and d) providing a fuel reformer located downstream of said fuel vaporizing chamber for receiving vaporized fuel from said fuel vaporizing chamber.
12. The method of Claim 11 wherein said atomizing section produces a fuel-steam mixture wherein the atomized fuel forms an annular film which surrounds a core of steam.
13. The method of Claim 12 wherein the atomized fuel film moves at a velocity which is about one half of the velocity of the steam core.
14. The method of Claim 13 wherein the respective velocities of the fuel film and the steam core are in the range of about 15 to about 153 m/sec.
15. The method of Claim 14 wherein said atomized fuel droplets have a mean diameter of less than about ten microns.
16. The method of Claim 15 wherein said super heated vaporizing stream is super heated steam or a mixture of super heated steam and air.
17. The method of Claim 16 wherein said super heated vaporizing stream is heated to a temperature of about 540┬░C.
18. The fuel processing assembly of Claim 17 wherein said fuel reformer is an autothermal reformer.
PCT/US1999/018875 1998-08-19 1999-08-19 Method and apparatus for injecting a liquid hydrocarbon fuel into a fuel cell power plant reformer WO2000010911A1 (en)

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JP2000566190A JP2002523862A (en) 1998-08-19 1999-08-19 Method and apparatus for injecting liquid hydrocarbon fuel into a reformer of a fuel cell power plant
EP99945099A EP1109736A4 (en) 1998-08-19 1999-08-19 Method and apparatus for injecting a liquid hydrocarbon fuel into a fuel cell power plant reformer
AU57788/99A AU5778899A (en) 1998-08-19 1999-08-19 Method and apparatus for injecting a liquid hydrocarbon fuel into a fuel cell power plant reformer
BR9914286-4A BR9914286A (en) 1998-08-19 1999-08-19 Fuel processing kit, and process for processing a hydrocarbon fuel

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